Note: Descriptions are shown in the official language in which they were submitted.
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HYDROGENATION OF ALUMINUM
USING A SUPERCRITICAL FLUID MEDIUM
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and the benefit of co-pending
U.S. provisional patent application Serial No. 60/873,105, filed December 6,
2006.
FIELD OF THE INVENTION
[0002] The invention relates to hydrogenation in general and particularly
to
a system and method that employs a supercritical fluid medium to hydrogenate a
metal.
BACKGROUND OF THE INVENTION
[0003] Hydrogen storage materials or media (HSMs) are a class of
chemicals containing hydrogen in a chemically or physically bound form. They
have wide potential utility in the areas of transportation, materials
manufacture and
processing and laboratory research. There is particular current interest in
HSMs for
the first application: vehicles powered by fuel cells or internal combustion
engines
for use in a 'hydrogen economy' will require an on-board source of hydrogen
fuel,
and hydrogen is very difficult to store either as a gas or as a cooled liquid
to
provide sufficient distance between refills.
[0004] Despite optimism over the last three decades, a hydrogen economy
remains a Utopian vision. The following criteria are identified for a viable
HSM:
1. High hydrogen storage capacity (min 6.5 wt % H).
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2. Low H2 generation temperature (Td ec ideally around 60-120 C).
3. Favorable kinetics for H2 adsorption/desorption.
4. Low cost.
5. Low toxicity and low hazards.
[0005] Alane, (A1H3),, is a polymeric network solid that contains 10.1
wt%
hydrogen and undergoes dehydrogenation to simple, nontoxic Al powder. It is an
excellent candidate material to meet the long term DOE hydrogen systems goals.
Since the time of filing of our earlier patent application entitled SYNTHESIS,
RECHARGING AND PROCESSING OF HYDROGEN STORAGE MATERIALS
USING SUPERCRITICAL FLUIDS (International Pat. App. PCT/CA2005/001908),
alane has become a serious contender as an HSM for vehicular hydrogen storage.
However, the enthalpy of dehydrogenation of all known phases of alane indicate
that
direct rehydrogenation can be accomplished only at extremely high pressures,
and is
therefore not viable as a large-scale technology. Thus the utilization of
alane as a
practically viable hydrogen storage material can only be realized if
alternative
methods can developed for the hydrogenation of aluminum. Currently, there are
no
methods known to achieve this outcome, aside from the laborious, costly and
wasteful
route involving conversion of Al into a corresponding halide or other
derivative,
followed by a metathesis reaction with a saline or complex hydride, as
detailed in
Equations 1 and 2.
Al + 3LiC1 + 1.5H2 AlC13 3LiH (uptake of H2)
Eq. 1
AlC13 3LiH Al + 3LiCI + 1.5H2
(release of H2) Eq. 2
[0006] These reactions can be applied in a cycle, as illustrated in
Scheme 1. It
is believed that the hydrogen uptake reaction given by Equation 1 converts the
Al +
3LiC1 to AlC13 + 3LiH by way of the intermediates Al + Cl2 + 3Li + H2 as shown
2
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on the left hand side of the cycle. It is further believed that the hydrogen
release
reaction given by Equation 2 converts the AlC13 + 3L1H to Al + 3LiCI by way of
the intermediates All-13 + 3LiC1 as shown on the right hand side of the cycle.
AlC13 +
H2 Al + C12 A1113+
-0- H2
3Li -1.- 1-12 3 LiC1
Al + 3LiCt*) Scheme 1
(0007} Reports describing the use of alane as a chemical reagent appear in
the
public literature at least as early as 1947. U.S. Patent No. 6,228,338 issued
May 8,
200] to Petrie et al. describes various methods of preparing alane using metal
hydrides as a source of hydrogen.
[0008j U.S. Patent No. 6,536,485 issued March 25, 2003 to O'Brien discloses
a means of room temperature packaging of hydrogen using a solvent such as
ethane or
hexane: large amounts of1-12 gas can be dissolved in these hydrocarbons when
they
are in a supercritical phase. O'Brien exploits the high miscibility of
hydrogen with
supercritical fluids, effectively using the organic solvent as an 11SM. Al
column 7,
lines 41-42 the patent teaches that by using the systems and methods disclosed
therein, The high weight of metal hydride type storing systems is also
avoided."
This statement appears to be teaching away from using metal hydrides for the
storage
of hydrogen.
SUMMARY OF THE INVENTION
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[0009] In one aspect, the invention relates to an apparatus for the
conversion
of aluminum to alane. The apparatus comprises a pressure vessel configured to
contain a quantity of aluminum powder or alane. The apparatus comprises
sources of
solvents (such as Me20, Et20 and THF), gases or liquids (or more generally,
fluids)
capable of attaining a supercritical state (such as CO2), and a source of
hydrogen
(such as gaseous H2) in fluid communication with the pressure vessel. As
needed, the
apparatus comprises a source of inert gas, which can be useful in excluding or
removing room air from the pressure vessel and other components of the
reaction
apparatus, so as to reduce the concentration of reactive gases such as oxygen
and
water vapor found therein to acceptably low levels. The apparatus comprises
one or
more pumps as needed to raise the pressure of fluids admitted into the
pressure vessel
to desired pressures. The apparatus comprises a heat source for heating the
pressure
vessel to a desired operating temperature and a cooler for cooling the
pressure vessel
to a desired temperature. The apparatus comprises a stirrer for stirring the
reaction
medium. The apparatus comprises a controller configured to control at least
one of a
fluid flow, a temperature and a pressure with the apparatus to fall within a
respective
one of a desired flow rate and direction, a desired temperature, and a desired
pressure.
In some embodiments, the aluminum contains (or is doped with) a dopant, such
as
titanium. In one embodiment, the controller is configured to control at least
one of a
fluid flow, a temperature and a pressure within the apparatus is a general
purpose
programmable computer-based controller.
[0010] In another aspect, the invention relates to a method of
generating alane.
The method comprises the steps of providing a pressure vessel; providing a
controller
configured to control at least one of a fluid flow, a temperature and a
pressure within
the apparatus to fall within a respective one of a desired flow rate and
direction, a
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desired temperature, and a desired pressure; introducing aluminum metal into
the
pressure vessel; reducing the concentration of unwanted reactive materials in
the
pressure vessel; introducing into the pressure vessel at least a substance
capable of
attaining a supercritical fluid state; introducing a source of hydrogen into
the
pressure vessel; raising at least one of the temperature and the pressure
within the
pressure vessel to attain a supercritical fluid state, and reacting the
aluminum with
the source of hydrogen to produce alane.
[0011] In one embodiment, the method further comprises the step of
introducing a solvent into the pressure vessel. In some embodiments, the
aluminum metal contains (or is doped with) a dopant (such as titanium). In
some
embodiments, the step of reducing the concentration of unwanted reactive
materials
in the pressure vessel is performed using an inert gas. In some embodiments,
the
substance capable of attaining a supercritical fluid state is CO2. In some
embodiments, the source of hydrogen is hydrogen gas. In some embodiments, the
solvent is an ether such as Me20, Et20, or tetrahydrofuran. In another
embodiment,
the method further comprises the steps of providing a molecule configured to
form
an adduct with alane; and after completion of the step of and reacting the
aluminum
with the source of hydrogen to produce alane, removing the molecule configured
to
form an adduct. The resulting product is substantially pure alane. In some
embodiments, the controller configured to control at least one of a fluid
flow, a
temperature and a pressure within the apparatus is a general purpose
programmable
computer-based controller, In one embodiment, the temperature is a temperature
below 100 *C.
[0012] The foregoing and other objects, aspects, features, and advantages
of
the invention will become more apparent from the following description.
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BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The objects and features of the invention can be better
understood with
reference to the drawings described below. The drawings are not necessarily to
scale,
emphasis instead generally being placed upon illustrating the principles of
the
invention. In the drawings, like numerals are used to indicate like parts
throughout
the various views.
[0014] FIG. 1 is a schematic diagram of an apparatus useful to carry out
a
reaction to generate alane, according to the invention.
[0015] FIG. 2 is an image of a commercially available reactor for
carrying out
reactions using supercritical fluids.
[0016] FIGS. 3 and 4 are pressure-composition-temperature (PCT) graphs
that
illustrate the progress of a dehydrogenation process for a specimen of
aluminum with
titanium hydrogenated under conditions similar to those described hereinbelow.
[0017] FIG. 5 is a gas chromatograph (GC) plot that illustrates the
release of
hydrogen from a sample of aluminum with titanium hydrogenated under conditions
similar to those described hereinbelow, in which the lower curve represents a
control
plot of the nitrogen carrier gas, and the upper curve represents the gas
desorbed by
heating the hydrogenated sample of aluminum with titanium in the presence of
the
nitrogen carrier gas.
[0018] FIG. 6 is an illustrative conceptual diagram of the 1:1 oxygen
donor
ligand adduct AIH3=Et20 .
[0019] FIG. 7 is an illustrative conceptual diagram of the 1:2 oxygen
donor
ligand adduct AIH3.2THF.
[0020] FIG. 8 is an illustrative conceptual diagram of the 1:1 nitrogen
donor
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ligand adduct A1H3.Me3N.
[0021] FIG. 9 is an illustrative conceptual diagram of the 1:2 nitrogen
donor
ligand adduct A1H3.2TEDA.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention relates to the use of supercritical fluids
(SCFs)
as a medium to effect the hydrogenation of aluminum, thereby forming alane.
Over
the past decade, SCFs have developed from laboratory curiosities to occupy an
important role in synthetic chemistry and industry. SCFs combine the most
desirable
properties of a liquid with those of a gas: these include the ability to
dissolve solids
and total miscibility with permanent gases. For example, supercritical (so)
CO2 has
found a wide range of applications in homogeneous catalysis, including such
processes as hydrogenation, hydroformylation and olefin metathesis.
Heterogeneous
catalyses carried out in scCO2 includes Fischer-Tropsch synthesis and
hydrogenation.
Furthermore, scH20 has also found wide utility in enhancing organic reactions.
[0023] Alane is a very attractive system for hydrogen storage, being a
simple
binary hydride containing 10.1 wt% hydrogen with a theoretical H density of
148 g/L,
and possessing a higher volumetric hydrogen capacity than liquid hydrogen. The
material is marginally stable at room temperature, releasing H2 between 60 and
140
C. Aluminum is cheap, safe and plentiful and is widely used in 21st Century
technologies. Alane thus clearly satisfies four of the five DOE criteria.
According to
the understanding prior to this invention, the major drawback is its lack of
reversibility: direct combination of Al and H2 requires draconian pressures ¨
in excess
of 25 kbar. The thermodynamic properties of AIH3 vitiate conventional gas-
solid
synthesis: A1H3 is thermochemically on the cusp with respect to decomposition
to Al
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and H2 (the cc-, 13- and y-phases of A1H3 have AHdehyd values of ca. +6, ¨4
and +1 kJ
ma', respectively). Thus, even at very high pressures of H2, the modest
thermal
input needed to overcome the activation barrier will place the system
thermodynamically in favor of the elements (Le. to the left of Eq. 3).
Al + 1.5 H2 A1H3 Eq. 3
[0024] SCFs have unique properties that allow us to overcome this
antagonistic interplay between the kinetic and thermodynamic properties of the
system. The total miscibility of H2 with a SCF is a distinct advantage in this
respect,
allowing effective concentrations of hydrogen equivalent to hundreds of bar to
be
attained easily and efficiently, and favoring the thermodynamics of AIH3 over
the
elements. In addition, conventional solvents may be added to the SCF medium to
enhance the solubility of reactants and/or products, allowing one to alter the
kinetic
and/or thermodynamic profile of the reaction (q.v.). This is particularly
important for
a system like A1H3 that is thermally fragile. Furthermore, the high
diffusivity of
permanent gases in SCF media encourages favorable kinetics to be established
close
to room temperature.
[0025] Examples of supercritical fluid systems and reaction conditions
that
can be used to produce alane by direct hydrogenation of aluminum include, but
are
not limited to: CO2 (75 bar), H2 (30-50 bar) 50-60 C, 2-4 h; dimethyl ether
(8 bar),
H2 (30-40 bar), 125 C, 2-4 h; ethane (65 bar), H2 (30-40 bar), 90 'V, 2-4 h;
and
ternary mixtures of Me20, CO2 and H2.
PREPARATIVE EXAMPLE
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[0026] FIG. 1 is a schematic diagram of the apparatus used to regenerate
alane
from a dehydrogenated sample of the material. In FIG. 1, there is shown a high
pressure reaction vessel I, which is in fluid communication by way of piping
and
valves with a Me20 cylinder 2, a CO2cylinder 3, a CO2 pump 4 and a H2 cylinder
5.
Customary symbols for valves are shown in the lines connecting the various
components of the apparatus.
[0027] A sample of alane prepared by conventional methods was doped with
TiC13 (2 mol%) in order to facilitate H2 evolution and absorption, then the
material
was dehydrogenated, giving a light gray powder. A powder X-ray diffraction
pattern
of the resulting material showed only peaks arising from Al. The material was
then
introduced into a 100 mL stainless-steel pressure reactor 1 under a blanket of
inert
gas. Examples of inert gases that are suitable for use in the systems and
methods of
the invention include helium, argon and nitrogen. Nitrogen having negligible
oxygen
content can be obtained as the boil-off gas from liquid nitrogen, or by
gettering
nitrogen over metal shavings heated to elevated temperatures (e.g., iron
heated to 800
C). See for example, LB. Milstein and L.F. Saunders, "Gettering of Gases for
High
Purity Applications," J. Crystal Growth 89, 124 (1988). A small amount of Me20
was admitted from tank 2 to vessel 1 as a vapor (50 psi) under its own head
pressure.
Liquid CO2 (890 psi) was next admitted to vessel 1 from tank 3 with the aid of
pump
4, and finally H2,(500 psi was added from tank 5 to vessel 1. The reaction
mixture in
1 was then heated to 60 C, thereby forcing the CO2/H2 mixture into a
supercritical
phase, and the contents were stirred at 150 rpm for I h. Preferably, a
temperature
below 100 C is employed. Suitable stirring apparatus can include any of a
mechanical stirrer and a magnetic stirrer. At this point, vessel 1 was cooled
to room
temperature and all volatile material was removed by venting and pumping, for
1 h.
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Reaction vessel 1 was then disconnected from the other components in FIG. 1,
transported into an inert atmosphere glove box, and opened. revealing a gray
powder,
albeit slightly different in color and appearance to the starting material.
[0028] In FIG. 1 features such as heating and cooling apparatus, vents
to allow
components or reagents to be removed from the system and controllers to
operate the
heating apparatus, the cooling apparatus and the valves are not shown.
Conventional
pressure sensing equipment that provides an electrical signal indicative of a
pressure
can be used to sense and to control pressures in the various portions of the
equipment.
Electrically or pneumatically operated valves can be used to control the
timing and
the flow rates as gases and fluids are moved from one container to another, or
are held
in a container, or are vented. Conventional electrical heaters and
conventional fluid
based (e.g., water) thermal exchange systems can be used to heat and cool the
reaction
vessel to the moderate temperatures required. Conventional thermal
controllers, using
sensors such as thermocouples, and feedback circuits that sense temperature
and
compare the temperature to a set point can be employed. In some embodiments,
conventional general purpose programmable computers can be used to implement
the
control functions for thermal control and for pumping, mass flow, and pressure
control.
[0029] In some cases, a person is permitted to control the valves and
the
operation of the apparatus. It is anticipated that higher yields of alane may
be
obtained. In particular, several factors could cause a reduction of the amount
of alane
measured as compared to the amount of alane produced in the process. First,
the
pressure of the system has to be reduced to remove the alane, thereby reducing
the
partial pressure of hydrogen available for equilibrium with the product, which
might
permit the product to decompose to some unknown extent. In addition, the
specimen
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to be examined is removed from the vessel I, and may be exposed to both oxygen
and
water vapor in the air ambient that is present during the analysis, even
though the
specimen is intended to be protected from reactive environments during the
analysis,
[0030] FIG. 2 is an image of a commercially available reactor for
carrying out
reactions using supercritical fluids. This reactor, and similar high pressure,
compact
laboratory reactors, are available from Parr Instrument Company, 211 Fifty
Third
Street, Moline, Illinois 61265-9984, or from several other sources. These
reactors can
be obtained with controllers that are used to monitor, control, datalog and
archive
various parameters, including temperature control, stirring speed control,
monitor
pressure, log data, control gas and liquid feeds and handle the product
produced. In
some instances a PC user interface is used to control one or more reactors.
[0031] FIGS. 3 and 4 are pressure-composition-temperature (PCT) graphs
that
illustrate the progress of a dehydrogenation process for a specimen of
aluminum with
titanium hydrogenated under conditions similar to those described in paragraph
[0026].
[0032] FIG. 5 is a gas chromatograph (GC) plot that illustrates the
release of
hydrogen from a sample of aluminum with titanium hydrogenated using scCO2 (-70
bar)/H2 (-35 bar), for 20 hours at a temperature of 60 C, in which the lower
curve
represents a control plot of the nitrogen carrier gas, and the upper curve
represents the
gas desorbed by heating the hydrogenated sample of aluminum with titanium in
the
presence of the nitrogen carrier gas,
ALTERNATIVE SYNTHESIS METHOD
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[0033] In a second method we expect that a doped supercritical CO2
reaction
medium can be used to prepare alane. We also expect that one can use a
completely
different supercritical fluid, to create a better thermodynamic environment.
[0034] It is expected that one can form an intermediate molecular alane
adduct, L.A1H3, whose enthalpy of complex formation (AHc) is more favorable
than
that of naked A1H3, and which can then be heated to temperatures close to
ambient to
remove the donor L and produce the desired polymeric (A1H3)õ material. We
believe
that the likelihood of this procedure working is high, as a similar two-stage
process is
employed to stabilize alane and then decomplex it in the so-called
`organometallic
route' that is currently the only method of making the material. t is expected
that the
donor molecule L, can be any one of a range of materials including ethers
(such as
Me20 and Et20) and amines (such as Me3N and Et3N). We expect that either or
both
of the 1:1 and 2:1 L.A1H3 complexes may serve as useful stabilized
intermediates in
the formation of alane. We expect that the addition of molecular hydrogen
transfer
catalysts (e.g. Wilkinson's catalyst) to the SCF reaction mixture may also be
effective,
in addition to the solid-state catalysts (e.g. Ti) incorporated in the Al
substrate.
[0035] As we have already explained, the marginal thermodynamic
stability of
alane has thwarted its direct preparation from Al and H2 according to the
reaction
shown in Eq. 3 given above, except under conditions of extreme temperature and
pressure. We expect that the use of alternative SCF media and mixtures with
donor
solvent or co-solvent capability, along with the use of hydrogen transfer
catalysts, will
allow the stabilizing of a molecular adduct of nL.A1H3 intermediate (with n =
1 or n
=2), while subsequent removal of the donor L and transformation to the
polymeric
binary hydride (Eqs. 4 and 5). It has already been demonstrated that
triethylenediamine (TEDA) can stabilize A1H3 sufficiently to permit direct
reaction
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between Al and H2 in conventk Aal hydrocarbon solvents to form polymeric
A11-13.TEDA. However, the strongly-bound TEDA ligand is not removable from
the AIH3 in this product, therefore rendering the adduct ineffective for
preparation
of pure alane. See "The Direct Synthesis of Amine Alanes." E. C. Ashby,
Journal
of the American Chemical Society, 1964, vol. 86, p. 1882.
Al (,) 1.5 H2 (g) 1.*A. Rh 0) --6*- (A1H3 )% 0) Eq. 4
21.. A
Al (0 + 1.5 142 w 2L.A1111 ---** (A1143 )x(1) Eq. 5
[0036] Examples of adducts that can be prepared (or that are believed to
be
capable of being prepared) include adducts using molecular oxygen donor
ligands
such as dimethyl ether (Me20), diethyl ether (Et20), dioxane, ethylmethyl
ether
(Me0Et), tetrahydrofuuran (THE), and molecular nitrogen donor ligands such as
pyridine, quinuclidine, trimethylamine (Me3N), triethylamine (Et3N), and
triethylenediamine (TEDA). Representative DFT-calculated energies of complex
formation (Alle) are given in Table I for oxygen donor ligands, and in Table
II for
nitrogen donor ligands, for the gas phase reactions described in Eqs. 6 and 7.
Ania + (9) Eq. 6
A 1H3 (1) 4, 21. (0 A1113.21 (6) Eq. 7
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[0037] FIGS. 6 through 9 are diagrams of illustrative conceptual
diagrams of
various one- and two-ligand adducts taken from the contents of Tables I and
II.
Table I
1:1 Complexes AHc (kJ/mol) 1:2 Complexes AHc (kJ/mol)
A1H3.Et20 -71.52 AIH32Et20
A1H3.Me0Et -77.68 AI113.2Me0Et -99.29
AlH3.Me20 -83.18 AIH3.2Me20 -113.69
AlH3.Dioxane -84.41 AIH3.2Dioxane -116.88
AlH3.THF -93.13 AIH3.2THF -122.02
[0038] FIG. 6 is an illustrative conceptual diagram of the 1:1 oxygen
donor
ligand adduct A1H3.Et20.
[0039] FIG. 7 is an illustrative conceptual diagram of thel :2 oxygen
donor
ligand adduct AIH3.THF.
Table II
1:1 Complexes AHc (kJ/mol) 1:2 Complexes AHc (kJ/mol)
A1H3.Et3N -89.02 A1H3.2Et3N
AlH3.Me3N -108.15 AlH3.2Me3N -145.80
A1H3.pyridine -109.24 A1H3.2Pyridine -142.12
A1H3.TEDA AlH3.2TEDA -155.56
A1H3.Quinuclidine -118.45 A1H3.2Quinuclidine -
156.24
[0040] FIG. 8 is an illustrative conceptual diagram of the 1:1 nitrogen
donor
ligand adduct AlH3.Me3N.
[0041] FIG. 9 is an illustrative conceptual diagram of the 1:2 nitrogen
donor
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ligand adduct AlH3.2 [IDA.
[0042] Various uses for alane material can be suggested, including
hydrogen
storage, provision of hydrogen recovered from alane, and use of alane fuses in
solid
fuels for booster rockets.
GENERAL PURPOSE PROGRAMMABLE COMPUTERS
[0043] General purpose programmable computers useful for controlling
instrumentation, recording signals and analyzing signals or data according to
the
present description can be any of a personal computer (PC), a microprocessor
based
computer, a portable computer, or other type of processing device. The general
purpose programmable computer typically comprises a central processing unit, a
storage or memory unit that can record and read information and programs using
machine-readable storage media, a communication terminal such as a wired
communication device or a wireless communication device, an output device such
as
a display terminal, and an input device such as a keyboard. The display
terminal can
be a touch screen display, in which case it can function as both a display
device and
an input device. Different and/or additional input devices can be present such
as a
pointing device, such as a mouse or a joystick, and different or additional
output
devices can be present such as an enunciator, for example a speaker, a second
display,
or a printer. The computer can run any one of a varietyiof operating systems,
such as
for example, any one of several versions of Windows, or of MacOS, or of Unix,
or of
Linux.
[0044] In operation, a general purpose programmable computer is
programmed with instructions in the form of software or firmware. The
instructions
control the operation of the general purpose programmable computer/ The
general
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purpose programmable computer can perform a variety of manipulations of data,
such
as mathematical operations (e.g., calculations), logical operations (e.g.,
comparisons,
or logical deductions following defined rules), and processing of textual or
graphical
data (e.g., word processing, or image processing). Data can be provided to the
general purpose programmable computer as recorded data or as real-time data.
The
result of any computation or processing operation is recorded in a machine-
readable
medium or memory for immediate use or for future use. For example, in micro-
processor based analysis modules, data can be recorded in a register in a
microprocessor, in a cache memory in the microprocessor, in local memory such
as
semiconductor memory (e.g., SRAM, DRAM, ROM, EPROM), magnetic memory
(e.g., floppy disc or hard disc) and/or optical memory (e.g., CD-ROM, DVD, HD-
DVD), or in a remote memory such as a central database. Future use of data
recorded
in a machine-readable medium can include displaying, printing, or otherwise
communicating the data to a user, using the data in a further calculation or
manipulation, or communicating the data to another computer or computer-based
device.
[0045] Machine-readable storage media that can be used in the invention
include electronic, magnetic and/or optical storage media, such as magnetic
floppy
disks and hard disks; a DVD drive, a CD drive that in some embodiments can
employ
DVD disks, any of CD-ROM disks (i.e., read-only optical storage disks), CD-R
disks
(i.e., write-once, read-many optical storage disks), and CD-RW disks (i.e.,
rewriteable
optical storage disks); and electronic storage media, such as RAM, ROM, EPROM,
Compact Flash cards, PCMCIA cards, or alternatively SD or SDIO memory; and the
electronic components (e.g., floppy disk drive, DVD drive, CD/CD-R/CD-RW
drive,
or Compact Flash/PCMCIA/SD adapter) that accommodate and read from and/or
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write to the storage media. As is known to those of skill in the machine-
readable
storage media arts, new media and formats for data storage are continually
being
devised, and any convenient, commercially available storage medium and
corresponding read/write device that may become available in the future is
likely to
be appropriate for use, especially if it provides any of a greater storage
capacity, a
higher access speed, a smaller size, and a lower cost per bit of stored
information.
Well known older machine-readable media are also available for use under
certain
conditions, such as punched paper tape or cards, magnetic recording on tape or
wire, optical or magnetic reading of printed characters (e.g., OCR and
magnetically
encoded symbols) and machine-readable symbols such as one and two dimensional
bar codes.
17
